High foaming antistatic detergent composition

ABSTRACT

A CLEAR HOMOGENEOUS, LIQUID DETERGENT COMPOSITION HAVING AN ANTI-STATIC CONDITIONING EFFECT ON HAIR, WOOL AND OTHER FIBERS IS DESCRIBED WHICH COMPRISES BY WEIGHT 5 TO 25% OF A TRIALKYL AMINE OXIDE CONTAINING AT LEAST ONE LONG CHAIN ALKYL RADICAL OF 10-18 CARBON ATOMS, 5 TO 25% OF AN ANIONIC SURFACE ACTIVE AGENT, 1/2 TO 10% OF A QUATERNARY AMMONIUM SALT HAVING AT LEAST ONE LONG CHAIN HYDROPHOBIC RADICAL OF 10 TO 20 CARBON ATOMS IN ITS MOLECULAR STRUCTURE AND 50 TO 90% OF INERT SOLVENT AND WATER. PREFERRED COMPOSITIONS CONTAIN SOAP AS THE ANIONIC SURFACE ACTIVE AGENT.

United States Patent Othce 3" Patented Jan. 1 6, 1 973 3,711,414 I-HGH FOAMING ANTESTATIC DETERGENT COMPOSITION Gordon Trent Hewitt, Upper Montclair, NJ, assignor to Colgate-Palmolive Company, New York, NY.

No Drawing. Continuation of abandoned application Ser. No. 454,173, May 7, 1965. This application Dec. 16, 1969, Ser. No. 882,396

Int. Cl. A61k 7/08; C11d 1/65, 3/44 US. Cl. 252-118 7 Claims ABSTRACT OF THE DISCLOSURE This application is a continuation of copending application Ser. No. 454,173 filed May 7, 1965, now abandoned.

This invention relates to detergent compositions containing quaternary ammonium salts.

Cationic surface active agents, well known in the art, have been employed as constituents of hair-conditioning and fabric treating compositions. When these agents are combined with anionic surface active agents in proportions to give homogeneous solutions, the cationic agents generally do not become adsorbed on the hair or fabric to an appreciable extent and the compositions do not foam well, particularly in hard water. By combining the cationic agents with selected amphoteric or non-ionic surface active agents, compositions which impart anti-static properties to hair can be produced, but such compositions have relatively poor foaming properties or have a noncosmetic feel during shampooing.

It is an object of this invention to provide a mixture suitable for use as a foaming detergent, such as a shampoo, which will also impart antistatic conditioning effects to hair, wool and other fibers.

Another object of this invention is the provision of a foaming detergent composition which is unaffected by hard water.

Still another object of this invention is the provision of a detergent containing soap and a cationic surface active agent which will foam in hard and soft water.

Other objects of this invention will be apparent from the following detailed description and claims. In this description and claims, all proportions are by weight unless otherwise indicated.

In accordance with one aspect of this invention, there is produced a detergent composition, particularly suitable for use as a hair-conditioning shampoo, containing a cationic surface active agent, an anionic surface active agent and a surface active amine oxide.

The cationic surface active agents employed in this invention are quaternary ammonium salts having a long chain hydrophobic radical. Especially effective are such compounds as oleyl or stearyl dimethyl benzyl ammonium salts. The oleyl or stearyl radicals may be replaced by other long chain alkyl radicals such as undecylenyl, lauryl, myristyl or cetyl, or by long chain radicals having other groups (e.g. aryloxyethyl groups as in diisobutyl phenoxyethoxyethyl dimethyl benzyl ammonium chloride); the

benzyl radical may be replaced by a substituted benzyl radical such as 3,4-dichlorobenzyl, 3,4-dimethylbenzyl, ethylbenzyl, etc., or by an alkyl radical such as methyl, ethyl, lauryl or stearyl (e.g. in di-long chain alkyl dimethyl ammonium chlorides, cetyl trimethyl ammonium bromide, oleyl dimethyl ethyl ammonium bromide, myristyl dimethyl 3,4-dichlorobenzyl ammonium chloride). The quaternary ammonium salt may have the nitrogen in a ring, e.g. in an N-oleyl N-ethyl morpholinium or N- pyridinium salt or N(laur0yl colamino formylmethyl) pyridinium chloride, or in an alkyl isoquinolinium salt (e.g. lauryl isoquinolinium bromide) or in an imidazolinium compound such as a l-methyl-l-alkylamidoethyl-Z alkylimidazolinium salt in which the alkyl groups have an average chain length of 17 carbon atoms.

In the preferred compounds there is a quaternary nitrogen atom directly linked to a carbon atom of a hydrophobic radical of at least ten carbon atoms (such as a long chain alkyl radical or an alkylaryl radical, in which there are 10-20 carbon atoms, for example), three valences of the nitrogen atom being also directly linked to other carbon atoms which may be in separate radicals (such as alkyl, particularly lower alkyl, or aralkyl radicals) or in a cyclic structure including the quaternary nitrogen atom (as in a morpholine, pyridine, quinoline or imidazoline ring). While the hydrophobic radical may be a simple hydrocarbon or hydrocarbon ether radical, it may also contain substituents such as halogen, and may even contain intermediate linkages, such as the amide and ester linkages of the higher alkanoyl colamino formylmethyl radical .RCOOCH CH NHCOCH although, as will be seen from the following examples, the presence of such amide or ester linkages is not at all essential in the practice of this invention.

The anion of the quaternary ammonium salt is most usually a chloride or methosulfate (OSO- OCH ion, but other ions may be used as is Well known in the art, e.g. bromide, phosphate, dialkyl phosphate, or acetate lOIlS.

The anionic surface active agent used is preferably a soap. The after-effects of any traces of material left on the hair are generally better, in soft water, when soaps are used than when other anionic surface active agents, containing sulfate or sulfonate groups, are employed in place of the soap. The use of hard water usually changes this, causing the deposition of a dull soap film; however, unlike the usual soap-containing compositions the preferred compositions of this invention foam well in hard water, as will be seen from the examples given below, even when the free fatty acid of the soap is present Preferred soaps are those of triethanolarnine, potassium, sodium, diethanolamine, morpholine and diglycolamine. The acid portion of the soap is advantageously that of a fatty acid such as lauric, myristic, stearic, oleic, elaidic, isostearic, palmitic, undecylenic, tridecylenic, pentadecylenic or other saturated or unsaturated fatty acid of 11 to 18 carbon atoms. Soaps of dicarboxylic acids may also be used such as the soaps of dimerized linoleic acid. Soaps of such other higher molecular weight acids such as rosin or tall oil acids, e.g. abietic acid, may also be employed. Other suitable anionic surface active agents are the carboxyl-containing amides of fatty acids with amino acids (e.g. the lauric acid amide of such amino acids as sarcosine, beta amino propionic acid, polypeptides from hydrolysis of proteins, isethionic acid or N- methyl tauric acid) and soluble salts of such carboxylcontaining amides.

Other anionic surface active agents which may be used are sulfates of fatty alcohols such as sodium lauryl sulfate, Turkey Red Oil or other sulfated oils, or sulfates of monoor di-glycerides of fatty acids (e.g. stearic monoglyceride monosulfate), alkyl poly(ethenoxy)ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1 to 6 ethenoxy groups per molecule); aliphatic sulfonates such as alkane sulfonates (e.g. sodium dodecane sulfonate), alkyl alkanoate ester sulfonates (eg. methyl ester of sulfomyristic acid) or lauryl or other alkyl glyceryl ether sulfonates; poly(ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol {usually having 1 to 6 oxyethylene groups per molecule). Also, but less desirably, the anionic surface active agent may be an alkyl benzene sulfonate such as sodium dodecyl benzene sulfonate.

It is preferred that the anionic surface active agents have hydrocarbon radicals of at least 10 carbon atoms, preferably long chain hydrophobic aliphatic radicals of about 11 to 18 carbon atoms. The cations of these surface active agents are advantageously such as to impart watersolubility to the acidic portion of the molecule or to maintainits water-solubility, e.g.'triethanolammonium or other alkanolamrnonium, potassium, sodium, magnesium (when the surface active agent forms a water-soluble magnesium salt), diethanolammonium, or (particularly when the blend is not acidic) ammonium.

A preferred amine oxide is lauryl dimethyl amine oxide. In place of the lauryl radical other long chain alkyl radicals, advantageously of about 10 to 18 carbon atoms, such as decyl, tetradecyl, cetyl, oleyl, hexadecyl or stearyl, may be employed. In place of either or both of the methyl radicals, there may be used an ethyl, propyl, hydroxyethyl, hydroxyethoxyethyl or hydroxy polyethoxyethyl radical. The long chain hydrophobic radical attached to the nitrogen of the amine oxide need not be only a hydrocarbon radical, It may, for example, contain other groups, such as carbonamide groups, such as in amine oxides of the formula in which RC is a long chain alkanoyl radical, n is a small whole number, and R and R are lower aliphatic groups; a specific example being the compound in which RC0 is the acyl radical of coco fatty acids, n is 2 and R and R are methyl.

The proportions of amine oxide and anionic detergent are advantageously each in the range of about -25% of the total aqueous detergent composition, and the weight ratio of these two components is advantageously in the range of about 1:4 to 4: 1. The proportions of the cationic agent are advantageously less than desirably in the range of about %.-5%' of the total aqueous detergent composition, preferably about 1 to 2%; the ratio of quaternary ammonium compound to anionic detergent may be, for example, in the range of about 2:3 to 1:10; for hair shampoos this ratio, for best results, is in the range of about 1: 4 to -1 10.

Best results in terms of antistatic effects on the hair are attained when the pH of the composition is below about 8 /2, preferably below about 8, eg in the range of about 5 to 7 /2. Homogeneity of the composition at such lower pHs is promoted by the use of relatively large amounts of the amine oxide and/ or cationic agent. Homogeneity is also promoted by the incorporation of water-soluble alcohols such as ethanol, propylene glycol, glycerol, sorbitol, hexylene-glycol, polyglycerol, dipropylene glycol or other polyols; these inert solvents are advantageously employed in concentrations up to 10%, e.g. in the range of about 3 to 10%.

As stated, the anionic-cationic-amine oxide compositions of this invention may be employed as shampoos, or as detergents for other fibrous material, particularly for fabrics of wool, silk or other protein fibers. Compositions of these components may also be used as foaming after-rinses, or conditioners for hair or fabrics. They may be used as anti-dandruff rinses or scrub soaps.

On dilution with water the homogeneous compositions become cloudy. It is believed that this may be due to the fact that there is present in the compositions a complex of the amine oxide and quaternary ammonium salt, with or without the anionic surface active agent, which complex is soluble above its critical micelle concentration but insoluble in dilute solution. The proportions of water and inert solvent in the homogeneous compositions are advantageously well within the range of 50- preferably about 60-80%.

Surprisingly, in the presence of the amine oxide and the quaternary ammonium salt it is possible to use a fatty acid, as such rather than in its soap form, to obtain a mixture which lathers well in water despite the absence of any soluble soap-forming cation. s is well known, reducing the pH (or adding free fatty acid) usually destroys the foaming properties of soap solutions. The unexpected effect also gives an advantage in the making of the soap-containing compositions, since it is here unnecessary, in contrast to previous experience with soap compositions, to carry out an accurate neutralization of the fatty acid to its soap form.

I have also observed that an otherwise cloudy, heterogeneous mixture of the anionic surface agent and amine oxide can becleared up and made homogeneous by the addition of the quaternary ammonium compound, as illustrated, for instance, in Examples 3(b) and 8 below.

The following examples are given to illustrate this invention further.

EXAMPLE 1 6% of triethanolamine oleate soap, 10% of lauryl dimethyl amine oxide and 2% of a cationic dispersing agent, consisting of oleyl dimethyl benzyl ammonium chloride, were dispersed in water. The mixture, which had a pH of 8.0, was clear. The pH was then reduced to 6.9 by the addition of a 50% aqueous solution of citric acid; the composition remained clear. Dispersions of the resulting composition in either hard or soft water gave large volumes of foam. When the composition was used for shampooing hair, it was found that a considerable proportion of the cationic dispersing agent was absorbed by the hair and that after shampooing and drying the hair was soft and smooth and had little or no tendency to acquire a static electrical charge and to fly apart.

EXAMPLE 2 10% of a soap, consisting of the triethanolamine salt of oleic acid, 9% of lauryl dimethyl amine oxide, and 1.6% of a cationic dispersing agent, consisting of oleyl dimethyl benzyl ammonium chloride, were dispersed in water. The resulting mixture, which had a pH of 8.2, was clear. The composition foamed well when it was dispersed in either hard or soft water; in contrast, when the amine oxide was omitted from the composition, the foam volume in soft water was much lower than when it was present, and the foam volume in hard water was considerably lower than that in soft water. When the composition was used for shampooing hair, it was found that, after shampooing and drying, the hair was soft and smooth and had little or no tendency to acquire a static electrical charge and to fly apart.

The composition of this Example 2 had an extremely low cloud point, i.e., 20 F. cloud/32 F. clear.

EXAMPLE. 3

(a) 3 parts of a 51% aqueous solution of oleyl dimethyl benzyl ammonium chloride were mixed with 60 parts of a 16.4% aqueous solution of triethanolamine salt of oleic acid. The result was a voluminous slimy white gel, having a pH of 8.3. When 27 parts of a 30% aqueous solution of lauryl dimethyl amine oxide were added, the mixture became a clear homogeneous solution having a pH of 8.2; when this homogeneous solution was added to a large volume of deionized water or hard water, it formed a blue-white turbid solution which foamed profusely.

(b) 10 parts of potassium salt of a mixture of 90% of the fatty acids of corn oil and 10% of the fatty acids of coconut oil and 10 parts of lauryl dimethyl amine oxide were mixed with 60 parts of water. When the pH of the mixture was lowered to 8.7, there was formed a heterogeneous opaque lotion. On addition of an aqueous solution of oleyl dimethyl benzyl ammonium chloride, the mixture became homogeneous.

EXAMPLE 4 10% of the sodium salt of the methyl ester of asulfomyristic acid,

CnHnCH-COOCH:

SOaNa 10% of lauryl dimethyl amine oxide and 1.5% of oleyl dimethyl benzyl ammonium chloride were dissolved in water. The resulting mixture was a clear solution having a pH of 7.8.

EXAMPLE 3 5 parts of myristic acid, 9 parts of lauryl dimethyl amine oxide, 2 parts of oleyl dimethyl benzyl ammonium chloride, 22 parts of water and 5 parts of ethanol (Specially Denatured, standard formula 40, containing t-butanol) were mixed to form a clear liquid of low viscosity which foamed well in water, despite the fact that the fatty acid was present as such and not as its soap. On dilution with 43 parts of water and addition of sufficient triethanolamine to raise the pH of the mixture to 7.4 (thus forming the triethanolamine soap of the myristic acid) there was produced a clear, homogeneous product with good shampooing properties.

EXAMPLE 6 To a mixture of 9.parts of lauryl dimethyl amine oxide, 5 parts of oleic acid, 1.54 parts of oleyl dimethyl benzyl aminoium chloride and 70 parts of water, there were added parts of ethanol (Specially Denatured, standard formula 40) and suificient triethanolamine to bring the pH of the mixtuer to 7 .8. The resulting mixture was clear. On acidification with a weak acid, i.e. citric acid (added gradually), it remained clear until the pH dropped to 5.7. It was noted that each time triethanol amine was added the pH rose promptly (by 1-2 pH units) then slowly drifted down, as if a slow physical rearrangement may have been occurring in the solution.

EXAMPLE 7 5 parts of triethanolamine myristate, 5 parts of lauryl poly(ethenoxy) ether sulfate having 3-4 ethenoxy groups per lauryl group, 9 parts of lauryl'dimethyl amine oxide and 1.5 parts of oleyl dimethyl benzyl ammonium chloride were mixed with 78 parts of water. The resulting clear mixture had a pH of 7.7.

EXAMPLE 8 10 parts of triethanolamine dodecyl benzene sulfonic and 10 parts of lauryl dimethyl amine oxide were mixed with 67 parts of water, 3 parts of oleyl dimethyl benzyl ammonium chloride, and 10 parts of-ethanol (Specially Denatured, standard formula 40). The resulting mixture was opaque; on addition of 3 additional parts of oleyl dimethyl benzyl ammonium chloride the mixture cleared.

EXAMPLE 9 (a) 10 parts of triethanolamine oleate, 9 parts of lauryldimethyl amine oxide and 1.5 parts of di-isobutylphenoxy-ethoxy-ethyl dimethyl benzyl ammonium chloride were mixed with 79 parts of water. The resulting solution, having a pH of 8.4, was clear.

(b) Example 9a was repeated, substituting 1.5 parts of stearyl dimethyl benzyl ammonium chloride for the 1.5

parts of quaternary ammonium salt of Example 9a. A clear solution having a pH of 8.3 was obtained.

In the foregoing examples, the simple fatty acids and their soaps may be replaced with more complex carboxylic acids or their corresponding soaps, particularly with the acids or soaps of the amides of amino acids (e.g. amides of fatty acids such as sarcosine, beta-aminopropionic acid or polypeptides obtained by hydrolysis of proteins, such as Maypons made with peptides from hydrolysis of collagen, the degree of polymeriaztion of the peptide being, for example, about 2-5). Example 10 illustrates one such formulation.

EXAMPLE 10 An effective hair shampoo was produced by mixing in water 10% of N-lauroyl sarcosine (free acid form), 6% of lauryl dimethyl amine oxide, 2% oleyl dimethyl benzyl ammonium chloride and sutficient triethanolamine to bring the pH to 7.0.

'In the foregoing examples perfumes and coloring agents may be added as desired. Generally only very small proportions of these will be examples, e.g. 0.3% perfume.

All the foregoing examples were carried out at room temperature, and atmospheric pressure, unless otherwise indicated.

The foaming abilities of the compositions of this invention may be measured by standard foam volume tests, on 1% solutions of the compositions. In such tests, the preferred compositions of this invention show foam volumes of over 175 ml. in deionized, zero-hardness water and over 150 ml. in water of hardness of 300 p.p.m. For example, the foam volume test on the 8.2 pH composition of Example 2 gives a foam volume of 205 ml. with zero hardness water and a foam volume of 202.5 ml. with water of 300 p.p.m. hardness.

The foam volume test referred to herein is a more accurate version of the well known Burrell Shaker Test. In the foam volume test, 5 grams of the composition to be tested are diluted with water to 500 cc. cc. of the solution is delivered, with precautions in handling to prevent foaming, to a straight-sided cylinder having a shallow rounded bottom and having a diameter of 54 mm. and a height of 260 mm., which cylinder is previously heated to a temperatuer of F. and maintained (with its contents) at that temperature throughout the test. The agitation of the solution in the cylinder is effected by means of a round disk of rigid plastic (Micarta) 3.95 mm. in diameter and 0.52 mm. thick, having 16 /8" drilled holes symmetrically placed in two circular patterns, 8 holes per circle. The disk is mounted horizontally, for up and down movement within, and concentric with, the cylinder, being fixed at the bottom of a vertically reciprocable A" stainless steel plunger rod and travelling a vertical distance of 171 mm., the lowest point of travel of the disk being at about the level, just above the bottom, where the crosssection of the cylinder becomes uniform. After the solution in the cylinder has reached the desired 105 F. temperature, the height of the liquid in the cylinder is measured, with the plunger rod at its lowest position so that the agitating disk is immersed in the liquid. The plunger and disk are then reciprocated, at a rate of 50 cycles per minute, for 3 minutes and the height of the top of the foam surface is measured at once, again with the plunger rod at its lowest position. The difference between the two measured heights is then converted to volumetric difference, and the result is termed the foam volume.

The water of 300 p.p.m. hardness is made by mixing 4.433 grams of CaCl .H O and 4.060 grams of MgCl .6H O

with sufficient distilled water to make one liter, followed by dilution of the resulting solution of 5000 p.p.m. hardness with suflicient additional distilled water to reduce the hardness to 300 p.p.m.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor Without departing from the principles and spirit of the invention.

What is claimed is:

1. A foaming detergent composition particularly suitable for use as a shampoo having an antistatic conditioning effect upon hair, wool, and other fibers which consists essentially of by weight:

(a) about to 25% of a trialkyl amine oxide containing a long-chain alkyl radical of about to 18 carbon atoms and two alkyl radicals selected from the group consisting of methyl, ethyl, propyl, hydroxyethyl, and hydroxyethoxyethyl;

(b) about 5 to 25% of a water-soluble, anionic, surface active agent selected from the group consisting of salts of higher fatty acids of 11 to 18 carbon atoms and salts of organic sulfate and sulfonate compounds selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, and alkyl alkanoate ester. sulfonates containing 10 to 18 carbon atoms in the alkyl group, said salt being selected from the group consisting of potassium, sodium, ammonium, diethanolammonium, and triethanolammonium salts, the weight ratio of said anionic detergent to said amine oxide detergent being in the range of about 1:4 to 4: 1;

(c) about /2 to 5% of a quaternary ammonium salt selected from the group consisting of alkyl or alkenyl dimethyl benzyl ammonium salts, dialkyl or dialkenyl dimethyl ammonium salts, N-alkyl pyridinium salts, N-alkyl morpholinium salts, said alkyl or alkenyl group containing 10 to 20 carbon atoms, and 1- methyl-1-alky1amidoethyl-2-alkyl-imidazolinium salts containing an average of 17 carbon atoms in the alkyl group, the weight ratio of quaternary ammonium salt to anionic detergent being in the range of 1:4 to 1:10;

(d) 50 to 90% of inert solvent and water, said inert solvent being present in an amount of 0 to 10% and being a water-soluble alcohol selected from the group consisting essentially of ethanol, propylene glycol, glycerol, sorbitol, hexylene glycol, polyglycerol, and dipropylene glycol;

said composition being in the form of a clear, homogeneous liquid having a pH of from about 5.0 to 7.5.

and F 2. A detergent composition in accordance with claim 1 wherein said quaternary salt is present in an amount of 1 to 2%.

3. A detergent composition in accordance with claim 1 wherein said quaternary salt is oleyl or stearyl dimethyl benzyl ammonium salt.

4. A detergent composition in accordance with claim 1 wherein said amine oxide is lauryl dimethyl amine oxide.

5. A detergent composition in accordance with claim 1 wherein said anionic surface active agent is said watersoluble salt of an organic sulfonate or sulfate compound.

6. A detergent composition in accordance with claim 1 wherein said anionic surface active agent is said watersoluble fatty acid salt.

7. A detergent composition in accordance with claim 6 wherein said salt is a triethanolamine salt.

References Cited UNITED STATES PATENTS 3,325,414 6/1967 Inamorato 252137 3,044,962 7/1962 Brunt et al 2521 10 2,734,830 2/ 1956 Hagge et a1. 117--47 3,325,404 6/1967 Cohen et a1 252-8.75 3,086,943 4/1963 Lang 252l52 2,950,255 8/1960 Golf 252152 2,828,772 3/1960 Anderson 252l53 X FOREIGN PATENTS 873,214 7/1961 Great Britain 2528.75 759,837 10/1956 Great Britain 252-547 OTHER REFERENCES Aromox Amine Oxides, Bulletin No. 6-25, published by Armour and Company, 1964, 9 pages.

Fatty Amine Oxides, by E. Jungermann and M. E. Ging, in Soap & Chemical Specialties, September 1964, pp. 59- 2.

Recent Advances in Fatty Amine Oxides, by T. P. Matson, J. Am. Oil Chemistes Soc., vol. 40, November 1963, pp. 640-642.

LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.

252-8.75, 8.8, 117, 153, 545, 547, 542, 550, 551, 554, 558, DIGEST 13, 14 

